Non-silver salt photosensitive materials

ABSTRACT

Photosensitive materials of excellent preservability which are not based upon a silver salt have a photosensitive layer comprising: 1. A HALOALKANE WHOSE BOND DISSOCIATION ENERGY IS LESS THAN 75 Kcal/mole; 2. A FURFURYLIDENE ACETAL COMPOUND 3. AN OPTIONAL PHENOL COMPOUND. The materials can be processed to form printing plates when the phenol compound is present. Such plates and processes are disclosed.

Umted States Patent 11 1 1111 3,904,419

Katsuyama et al. a 5] Sept. 9, 1975 [54] NON-SILVER SALT PHOTOSENSITIVE 3,647,448 3/1972 DeMeyer et a1. 96/90 R 3,745,012 7/1973 96/90 R 3,753,718 8/1973 96/90 R [75] Inven ors: H r ml K s yam Mln ml- 3,773,515 11/1973 Yamashita et a1. 96/90 R ashigara; Hisatake Ono, Saitama, Asaka both of Japan Primary ExaminerJ. Travis Brown [73] Assignee: Fuji Photo Film C0., Ltd., Attorney, Agent, or Firm-Siighrue, Rothwell, Mion,

Minami-ashigara, Japan Zinn and Macpeak [22] Filed: May 25, 1973 [21] Appl. No.: 364,167 [57] ABSTRACT Photosensitive materials of excellent preservability [30] Foreign Application Priority- Data which are not based upon a silver salt have a photo- May 26, 1972 Japan 47-52264 Sensitive layer comprising June 8, 1972 Japan 47-57105 a haloalkane Whose bond dissociation energy is less than 75 Kcal/mole; 52 us. 01 96/90 R; 96/33; 96/48 R 2. a furfurylidene acetal compound 51 111:. c1. 603C 1/52; G03F 7/02 an optlonal Phenol compound- [58] Field of Search 96/90 R, 33 Th aterial can be processed to form printing plates when the phenol compound is present. Such plates [56] References Cited and processes are disclosed.

12 Claims, No Drawings BACKGROUND or THE IN'V NTI v 1. Field OfThe Invention I are those furfurylidene acetal compound of the followsensitive materials, printing plates made therefrom and,

to a process for formingsuch printing plates.

2. Description Of The Prior Art When furfural is heated under .acidic conditions, a l7 waterinsoluble dark substance is formed (described in Handbuch der organischen Chemie (written by Beilstein), Vol. 17, page,2 74)., I

When furfural is reacted with a phenol type com pound, a dark furfural-phenol resin is formed. (dc-. scribed in Encyclopedia of Polymer Science and Technology, Vol. 7, pages 432445).'

However, when furfural is stored in a room, it

gradually blackens to beconie a resin,and, therefore, it is difficult to manufacture photographic materials using furfural. Light sensitive materials utilizing the-light sensitivity of a lower haloalkane are known, for example, haloalkane-aromaticamine type photographic media as described in Light-Sensitive Systems (written by J. Kosar), Chapter 8, or lower haloalkanefurfurylidene compound-primary aromatic amine type photographic media as described in Japanese Patent 259 52/7l-and US. Pat. No. 3,394,395.-In theformer, triphenylmeth-. ane dyestuffs form color images. In the latter, Stenhouse dyestuffs which are the reaction products of aldehydes derived from the furfurylidene compounds and amines form color images.

The above mentioned aromatic amines are easily oxidized. For example, when they are left in the air," they gradually blacken. Therefore, these aromatic amines are unsuitable for practical use in light-sensitive materials, since they have such defects that they often stain the background of the materials. I I

SUMMARY CKJFYTHE INVENTION An object of the present invention is to provide'no'n isto, ro- I .1. The present invention relates to non-silver salt photov v (wherein X represents a halogen atom (where Xs may 'diff'er from .each other)or a hydrogen atom (but all X's 1 ing formula (Ila) or (IIb);

' "Ii-ox,

cannot be hydrogen atoms), and R represents a .hydrogen atompa halogenatom;-an alkyl' group having I 7 carbon atoms; a halogen substitutedalkyl group having l- 7'carbon atoms; an acyligroupg or'an acyl group or V wherein R and R each represents ,one or.-two phenyl grups or one or two aralkyl groups (having 69 carbon atoms) (Where the phenyl or aryl ring in the aralkyl group can be substituted with a halogen atom or an alkoxy group having 1-3 carbon atoms), or one or two furfuryl groups,

vide non-silver salt photo-sensitive materials which may convert the formedlatent image to a ,visible image in a wide range of temperature. r

Yet another object of the present invention is to provide novel printing plates and a method of making printing plates.

The inventors made various studies in order to eliminate the drawbacks of the above mentioned conventional non-silver salt photosensitive materials, and at last have found that it is preferred to use furfural resins or furfural-phenol resins as the image forming component, and to use the furfural-phenol resins for printing plate production.

More precisely, the above mentioned objects of the present invention are attained by using alight-sensitive layer containing a light-sensitive haloalkane, preferably of the following formula (I), having a bond dissociation energy of less than 75 Kcal mole. Preferred materials (Ilh) wherein R represents an alkyle ne group having 27 carbon atoms, which can be substituted with a hydroxy- 1 where R represents a methylene chain of 23 carbon atoms whichcan be substituted byan alkyl group of l-4 carbon atoms,a hydroxyalkyl group of l-4 carbon atoms or an imino group, and which can be dimerized via a spiro-carbon atom as described above.

The light sensitive layer of the present invention preferably contains, in addition to the light-sensitive haloalkane of the'above formula (I) and the furfurlidene ace-' (Illa) R (IIIb) wherein n is an integer of l3, and R representsa hydrogen atom, a. halogen atom,-an alkyl group of-.l4

carbon atoms, an alkoxy group of l4 carbon atoms, a

carboxyl group, an alkoxycarbonyl groupof 1-12 carbon atoms, a formyl group, a sulfo group (SO H), an. amino group or an acyl group of l4 carbon atoms. The

amino group is not preferred for the non-silver salt pho tosensitive material per se.

Printing plates are formed by image-wise exposing an element having a photosensitive layer containing a photosensitive haloalkane, a furfurylidene acetal compound and a phenol compound represented by the above formulae to light, uniformly heating the photo- DETAILED DESCRIPTION OF THE INVENTION The haloalkane represented by the above formula (I) releases a halogeno radical, and this takes out a hydrogen atom from a solvent and the like to form a hydroh'alogenic acid. Accordingly, a large amount of 40 acids exist on the image-exposed part as a latent image. On the other hand, the furfurylidene compound is activated in the presence of the thus formed acid which acts as a catalyst to be converted into a image-like furfural resin of black or dark shade.

The haloalkanes used in this embodiment of the present invention include these compounds whose bond dissociation energy (energy to produce the firsthalogen free-radical) is less than 75 Kcal/mole, preferably those whose bond dissociation energy is less than 70 tolylsulfon'e, 68,6i5a-tribromo-p nitroacetophenone and 01,01,01-dibromo-p-methylacetophenone, etc. Further, halogen containing compounds which form halogen radicals upon exposure to light or form halogeno-acids in the presence of phenol compounds may be used.

In the non-silver salt photosensitive material per se, the following are preferredi carbon tetrabromide, iodoform, carbon tetraiodide hexachloroethane, hexafluoroethane, 1,2-diiodoethane, bromotriiodomethane, chloro-diiodome thane, etc, which are solid at room temperature, and in particular, carbon tetrabromide' and iodoform are preferred.

The furfurylidene compound to be used in the present invention may easily be synthesized by the reaction of furfural and an alcohol.

For instance, difurfurylidene pentaerythritol can be prepared by refluxing l molequivalent of pentaerythritol and 2 mol equivalents of furfural in toluene in the presence of a catalytic amount of p-toluenesulfonia acid, e.g., l/ 1000 mol equivalent to reactants, removing 2 mol equivalents of water from the azeotropic mixture by means of a quantitative water receiver (Distilling Tube Receiver 0 41 l Shibata Kagaku Kikai Kogyo) and pouring the reaction mixture into a large amount of water to precipitate the product. All furfurylidene acetal type compounds among the furfurylidene compounds can be synthesized by the above process merely by altering the starting materials.

For example compound Compound 1 can be produced as follows: furfural 2 mols( 192g), pentaerythrytol 1 mol (136g) and p-tolu'ene sulfonic acid 0.2g were heatedand refluxed in a distilling tube receiver equipped 2l flask provided with a cooling tube, 11 of benzene being used as the solvent. As the reaction proceeded, water appared 'in the .receiver (described above), the reaction mixture became black, and some precipitation appeared. After the water was frictionally distilled the reaction product was filtered, and the filtrate poured into 31 of ligroin, whereupon flaked crystals appeared. 200 g of yellow crystals (mp. l6l3C) of Compound 1 were thus obtained.

In the following, examples of the furfurylidene compounds used in the present invention are shown.

CH C b as i y pro \OCH2 \CH2O/ carbon) 0 l O aiodohexane, hexabromoheptane, a,a,oz-tri- A bromoacetophenone, a,a,a-trichloroacetophenone, Difurfurylidene pentaerythritol a,a,a-p-tetrabromoacetophenone, a,a,atribromomethylphenylsulfore, a,a,a-tribromomethyl-p- (dimcrization o -cn c. H

O-CH-, CH OH o 5 O-CH Furfurylidene 2-ethyl-2-hydroxymethyll ,3-

propylene ether. 1 3. CH

OCH mil ll o Furfurylidene dibenzyl ether. CH 8. o

Furfurylidene difnrfuryl ether.

o-cH. o I

I Q I 20 l /O-CH2 OCH Furfurylidene dianisyl ether.

9. o cH. cH., I

OCH N c O 0-CH. I 2

CH 4O Furfurylidene Z-methyl-2-furfuryhdene1m|no-1,3- O propylene ether. 1

- Furfurylidene dibenzhydryl ether. 0C 10. CH

CH l o Furfurylidene tetramethylethylene ether. OCH2 6.

O Furfurylidene bis-(p-chlorobenzyl) ether.

The non-silver salt photo-sensitive materials of the present invention preferably consist of a support and of a light-sensitive layer applied on the said support and containing the above mentioned components. The light-sensive layer may further contain a film forming Furfurylidene diphenethyl ether. binder. In many cases, the said layer preferably contains the binder (especially to form a printing plate, however). The binder may be anyone of the known binders such as nitrocellulose, benzyl cellulose, polycarbonate, polyvinyl acetate, cellulose acetate, cellulose acetate-butyrate, cellulose acetatephthalate, polyvinyl chloride, polystyrene, polyester, polymethylmethaacrylate, polyvinyl-pyrrolidone, polyvinyl-butylral, polyphenyleneoxide, etc. It is to be noted that the heating range for fixation may vary, depending upon the se lection of the binder and the combination thereof. Binders as are used in the printingplate embodiment are preferably resistant to temperatures less than 200C and do not react with the compounds of the layer.

As earlier indicated, the objects of the present inven' tion may further preferably be attained, by incorporating a phenol type compound of the formula (Illa) or formula (IIIb) in the above mentioned light-sensitive layer.

for example, pyrogallol, methyl gallate, ethyl gallate, n-propyl gallate, isoamyl gallate, lauryl -gallate stear yl gallate, gallic acid, phloroglucinol, 2,4 ,6-trihydrxytoluene, 2,4,6-trihydroxyacetophenone, 3-methoxycathechol, 3,4-dihydroxy-benzoic acid, 2,5- dihydroxybenzoic acid, 2,6,-dihydroxy-3,5-di-tert.butyl benzoic acid, 2,6-dihydroxy benzaldehyde, 4,5-dihydroxytoluene, resorcinol, 4-chloro-resorcinol, 3,5- dihydroxy-toluene, hydroquinone, p-hydroxybenzene- CHO sulfonic acid, p-bromophenol, l,5 -dihydroxynaphthalene, l,5-dihydr0xy-naphthalene, 1,3-dihy droxy-naphthalene, 2,7-dihydroxy-naphthalene-3- sulfonic acid, etc. 2,4-dihydroxy-5-bromobenzoic acid can also be used, but is non-preferred in the non-silver salt photosensitive material per se embodiment.

Due to the use of the phenol type compound, it is possible to extremely increase the imagedensity, which is, however, somewhat insufficient in the-layer comprising a halo-alkane and a furfurylidene compound only. This action of the phenol type compound is higher with the increase of the hydroxyl groups therein. From this view-point, the phloroglucinol derivative is in particular preferred. Another merit due to the use of the phenol type compound is that the latent image is colored in yellow, orange or pink tone, depending upon the constitution of the layer. Accordingly, is possible to change the latent image to a colored one, and thusthe photographic materials containing the phenol type compound are preferable to the formation of various kinds of desired images. l

The action of the phenol type compound is supposed as follows: It is considered that the halo-alkane and the phenol compound form a benzene type dye via dehydrohalogenation reaction therebetween according to the following reaction formula: g

3 light CBr H The representatives of the phenol type compounds,

When a light-sensitive material containing a dispertant action in the light-sensitive system of the present invention. In the next place, when a furfurylidene com- 10 pound is applied to the above mentioned specimen wherein a benzene type dye is formed, and then is heated, only-"the part wherein the dye is formed is blackened "in dark. That is, it is considered asfollows: A great amount of acids are formed in the part'of the 15 latent image, and thus the furfurylidene compound is converted to furfural due to the catalytic action of the said acid, andafterwards, the furfuralbeingsto react with a phenol compound to form a furfural-phenol resin. The rnechanism on the formation of the furfuralphenol resinis as follows, referring to Kunststoffe (written by Koschulz) Vol. 23 (1933), page 97: In the first place, a precondensation reaction proceeds between the furfural and the phenol compound, according to the following reaction formula, and the resulting precondensation product is converted under heating to a dark resin or a furfural-phenol resin having a ternary network structure, via the ring cleavage polymerization of the furan ring.

In the light-sensitive mateirals of the present invention comprising the above mentioned lower haloalkane, furfurylidene acetal compound and phenol 40 compound, the lower halo-alkane is reacted with the phenol compound byexposure to release a hydrogen halide, and the resulting hydrogen halide acts to hydrolyze the furfurylidene acetal compound to furfural. In the next place, the thus formed furfural is reacted with the phenol compound to form alprecondensation prodand as a coloring agent.

The light sensitive materials of the present invention are prepared by dissolving a halo-alkane, a furfurylidene acetal compound and optionally a film forming binder, and further optionally a phenol type compound 5 (the latter two components being used for a printing plate) in an organic solvent (such as toluene, benzene, dioxane, alcohol, tetrahydrofuran, chloroform, methylethylketorie, ethyl acetateor the like), and then applying the resulting solution on a support.

0 For best results, the haloalkane'having a dissociation energy of less than 75 kcal/mol, preferably less than Kcal/mol, isjpresent in an amount of fromabout 0.01

i c: 4am

to about 100 g/m of support. Generally, in the printing plate embodiment, it is preferred to use from 0.5 to 10 g/m of support, whereas in the non-silver salt photosensitive material embodiment it is acceptable to use somewhat lesser amounts, i.e., where one merely desires to form an image, and in thiscase, a preferred amount of haloalkane is from 0.2 to 0.5 g/m These ranges can, of course, overlap, but, generally speaking lesser amounts will be used in image formation per se and somewhat greater amounts in printing plate formation, where layer removal is mandatory. For best results, per one weight part of haloalkane, the following component weight parts are used: furfurylidene acetal, ca. 0.05 to ca. 50, preferably 0.ll; phenolic compoumd, ca. 0.05 to ca. 100 preferably 0.1-20; and film binder ca. 0.03 to ca. 10, preferably 0. l5. Such a sys tem is easily applied from a solvent in an amount of ca. 10 to ca. 5,000, preferably 50500, same basis. The above ranges find most special application to the printing plate embodiment.

In the non-silver salt photosensitive material embodiment, however, the weight ratio of the haloalkane to the furfurylidene compound is preferably 0. l3, better yet 0.5-2, and the weight ratio of the phenol type com pound to the furfurylidene compound is preferably 5 or less, better yet 0.05-2. The amount of the binder to be used is not specifically limited, and is sufficient to be able to carry the respective components. However, a preferred ratio by weight of haloalkane to binder is within the range of from about 0.03 to about 10, preferably from 0.1 to 5, weight parts of haloalkane to weight part of binder.

The support may be anyone which has been conventionally used in this field, for example, paper, a plastic film or a metal plate such as aluminum plate or the like. As for the paper support, baryta paper or a paper coated with a high molecular compound (such as polyethylene, polyvinyl alcohol) is in particular preferred.

The thickness of the film coated for the lightsensitive layer is, in general, 0. l50 .1., most preferably llO p. for the non-silver salt embodiment. Excellent results are obtained in the printing plate embodiment when the thickness of the photosensitive layer is about 0.1 to about 30 .1., better yet 0.5 to p..

For printing plate formation, however, the surface of the support should be hydrophilic so as to function as a printing plate. If the support selected is not inherently hydrophilic, the surface of the support can be so rendered by known methods such as chemical treatment, graining, anodizing, the application of a hydrophilic layer thereto, etc.

There is no substantial limitation on the support so long as it is not excessively deformed at the heating conditions used or deteriorated by the solvent used. The degree of hydrophilicity illustrated by the support is not overly important so long as it is generally in accordance with degrees of hydrophilicity used in prior 'art printing plates.

When an image is formed by using the photosensitive material of the present invention, the said material is exposed image-wise by means of a light of 3000-6000 A wavelength and then is heated at a temperature ranging from room temperature to 200C. Preferred heating conditions are within a range of from about 50 to about 150C for about 30 seconds to 5 minutes. The heating is performed for the purpose of the resin formation (that is. reaction acceleration) and of the removal of the remaining halo-alkanes (that is,

fixation), and the time for the heating may freely be determined. As the case may be, even though the heating step is omitted, 21 permanent image can be formed.

to light of a wavelength of about 3000 to preferably 5000 A. Electromagnetic waves Whose wave have length is less than 3000 A-can also be used. The exposure can be carried out by means of a mercury lamp or the like, e.g., xenon lamp etc. The exposed material is then uniformly heated to a temperature of from room temperature to about 200C. In general, heating is for from several seconds to 20 minutes, with standard heating being for 30 seconds 5 minutes at C or so for superior printing plate formation. The heating may be carried. out with 2.5-20 u infrared irradiation.

In the printing plate embodiment, images which are distinguishable are then treated with a solvent in order to remove parts unnecessary in the printing plate (namely, non-printing or unexposed parts) so as to expose the hydrophilic surface of the support. The solvent used can be suitably selected on the basis of the binder used. The solvents used include, for example, alcohols, preferably C C alcohols, such as methanol, ethanol, propanol, butanol, cyclohexyl alcoholand ethylene glycol, ketones, preferably C C ketones, such as acetone, methylethyl ketone and cyclohexanone, aromatic solvents, preferably C.,C aromatic solvents, such as benzene, toluene and'xylene, ethers, preferably C C ethers, such as diethyl ether, dioxane and tetrahydrofuran, and esters, preferably C,,C esters, such as ethyl acetate, ethyl formate and y-butyrolactone.

Good results are obtained at the following solvent treatment conditions: temperature, ca. 30 to ca. 200C, preferably 50-l50c, time, ca. 2-3 sec. to ca. 10 min., preferably 30 sec. 5 min., pressure, 1 atm., though sub or super atmosopheric pressures can be used.

According to the present invention, good printing plates having excellent printing durability can be produced by exposure to light, heating and solvent treatment. Further, since visible images resulting during production of the printing plate, inspection of the printing plate can be easily carried out.

In the present invention, the used furfurylidene compound is quite stable, and thus the resulting photosensitive materials are excellent in preservability for a long period of time, and moreover, an image with less background stain can be formed. Furthermore, a permanent image can be obtained, as the case may be, only by' the operation combined with the heating step, and the obtained image has excellent properties such as high weather resistance, high chemical resistance and the lime, that is, any bleeding or fading does not occur in the image. Thus, the photo-sensitive materials of the present invention have various merits which could not be attained in the conventional photo-sensitive materials for forming colored images.

Now, the present invention will be explained more in detail in the following examples where: Examples l5 deal with the non-silver salt photosensitive material per se and Examples 615 deal the printing plate embodiment.

In the Examples, all percentages are by weight, unless otherwise indicated.

EXAMPLE 1 After 0. lg of difurfurylidene-pentaerythritol and 0. lg of iodoforrn were dissolved in 3g of a 5% polystyrene-benzene (polystyrene of an average polymerization degree of about 900) solution, the resulting solution was applied to a photographic baryta paper using a coating rod, and then dried for 30 minutes in a drying chamber at 70C to prepare a light-sensitive material (light sensitive layer: ca 3 ,a thick).

The thus prepared light-sensitive mateiral was con tacted with a negative film, and exposed for 20 seconds by means of a diazotype duplicator with a built-in 600W mercury-vapor lamp at 20 cm. distance, whereby a yellow image was obtained (main wavelength: 3650 A).

Next, the material was heated for 120 seconds at 120C to obtain a brown image having a reflection density of 1.35. The background of the material was colorless. When the material was exposed to sun-light for one day, the background colored yellow while the image was unchanged.

EXMAPLE 2 0. lg of difurfurylidence-pontaerythritol, 0. lg of carbon tetrabromide and 0.1g of phloroglucinol were dissolved in 3g of a 5% polystyrene-tetrahydrofuran (polystyrene of an average polymerization degree of about 900) solution, and the resulting soultion was applied to a photographic baryta paper using a coating rod and then dried for minutes in a drying chamber at 50C (light sensitive layer ca. 3 ,u. thick).

The resulting light-sensitive paper was closely contacted with a negative film, and exposed for seconds by a diazotype duplicator with a built-in 600W mercury-vapor lamp 20 cm from the element, whereby a positive image colored a strong dark green color was obtained. The reflection density of the formed image was 1.41.

Next, the paper was heated for 30 seconds at 1 10C, whereby the color of the image changed to blackish, and the reflection density thereof increased to 1.86. There was no stain in the background of the paper.

When the material was left in a light room without exposure to direct sun light, the color did not change and the background was not stained.

When the material was continuously exposed to direct sun-light for one week, the color image was not changed, but the background somewhat colored pale Time for exposure (seconds) 25 12.5

Time for heating (seconds) 10 10 l0 10 Optical density 0.99 0.75 0.61 0.33

EXAMPLE 3 0.1g of difurfurylidene pentaerytyritol, 0.1g of iodoform, 0.1g of pyrogallol and 3g of a 10% polyvinyl butyral-tetrahydrofuran (polyvinyl butyral: about 700 average polymerization degree) solution were coated to prepare a light-sensitive paper (3 thick light sensitive layer), and the resulting paper was exposed, as in Example 2, whereby an image of orange color was formed on a background of a pale-yellow color. The resulting paper was heated for 30 seconds at 100C, whereby the color of the image changed to a dark black-brown color.

Separately, a light-sensitive paper prepared as above except using only 0.1g of iodoform and 0. *1 g of pyrogallol was exposed to light. Although an image of orange color was obtained, the color of the resulting image faded to a pale yellow color after heating under the same conditions as above.

EXAMPLE 4 0. lg of furfurylidene acetal, 0.1g of a haloalkane and O. 1 g of a phenol type compound were dissolved in 10% resin solution, as identified in the following Table. The resulting solution was applied to a baryta coated paper and dried to provide a light sensitive layer 4 a thick as in Example 2. The thus prepared light-sensitive matebrown. 45 rial was exposed and heated as in Example 2.

furfurylidenc haloalkane phenol type high molecular color compound compound weight hinder (resin) difurfurylidenecarbon gallic acid polystyrene* brown pentacrythritol letrabromide " n ethyl gallatc olive brown 1,5-dihydroxynaphthalene yellowishbrown iodoform 2,4,6-dihydroxypolyvinyldark acetophenone hutyra1* green 2,4,6-dihydroxydark toluene green furfurylidenecarbon phloroglucinol polystyrene dark 2-ethyl-2- tetrahromide green hydroxymcthyl- 1,3-propylene ether furfurylidcncphloroglucinol black furfuryl alcohol Continued furfurylidene haloalkane phenol type high molecular color compound compound weight hinder (resin) furfurylidencphloroglucinol dark 2-mcthyl-2- green furfurylidene imino- I ,3- propylene other furfurylidencpyrogallol hrown diphcnyl cthcr "average polymerization degree about 900 average polymerization degree ahout 700 EXAMPLE EXAMPLE 7 01g of difurfurylidene-pentaerythritol, 0.1g of carbon tetrabromide and 0. lg of a phenol type compond were dissolved in a 5% polystyrene-tetrahydrofuran solution (same as Example 2) and treated as in Example 2 to obtain a light-sensitive material. The material was exposed to light for 30 seconds using a 600W diazotype duplicator 20 cm from the material (main wavelength 3650 A) to form a visible latent image colored pale brown. After heating for 60 seconds at 1 C. a brown image having a reflection density of 0.5-0.9 wasobtained. The phenol type compound added to the lightsensitive material to form a series of different elements was as follows: methyl gallate, propyl gallate, isoamyl gallate, lauryl gallate, 3-methoXy-catechol, catechol, 2,5-dihydroxy-benzoic acid, 3,4-dihydroxy-benzoic acid, 2,4-dihydroxy-5-bromobenzoic acid, 2,6-dihydroxy-benzaldehyde or p-hydroxy-benzene-sulfonic acid.

EXAMPLE 6 A prining plate making material was prepared by dissolving 0. lg of carbon tetrachloride, 0. lg of difurfurylidene pentaerythritol and 0.1g of phloroglucinol in 3g of a 5% tetrahydrofuran solution of polyvinyl butyra] (Eslex BM 5, Sekisui Kagaku), and applying the resulting solution to an anodized aluminum plate. The thickness of the photosensitive layer was 2 1.4.. The anodization conditions were: 40% phophoric acid, room temperature, l0 A/cm electric current supplied for 2 minutes. This is a conventional art procedure.

A negative film was brought into physical contact with the resulting plate making material. The printing plate making material was then exposed to light from a 600W mercury lamp at a cm distance through a pylex filter for 20 seconds whereupon a positive printing-out image was formed.

This printing plate making material was then heated for one minute on a heating plate at l 10C, whereupon the positive printing-out image changed to a dark brown color image, By washing with methanol at room temperature for 1 minute, unexposed parts were removed, i.e., peeled off. Upon further washing with water, a printing plate for negative working was obtained, in which the exposed parts remained as a brown image.

Though this printing plate could be utilized as it was on a printer, it was possible to increase the oleophilic property of the image part and to improve the abrasion resistance by applying a lacquer thereto. Further, the hydrophilic property of the non-image part was improved by a rubbering treatment.

A printing plate making material was produced by dissolving 0. lg of carbon tetrabromide, 0.2g of difurfurylidene pentaerythritol and 0.6g of phloroglucinol in 9g of a 5% tetrahydrofuran solution of polyvinyl butyra (Eslex BM 5, Sekisui Kagaku), and applying the resulting solution to an anodized aluminum plate. The thickness of the photosensitive layer was in the range 1-4 a.

After putting a positive film on the resulting printing plate making material, it was exposed to light in the same manner as in Example 6 and treated by heating at l 10C for 2 minutes. A deep dark-green image appeared on the surface of the printing plate making material.

The printing plate material was then washed with ethyl alcohol at room temperature for 2 minutes and then with water at room temperature for 2 minutes. A printing plate for positive working was thus obtained.

Further, the printing plate was treated with a development ink in order to improve the olephilic property of the image parts, whereby a positive image was formed. When the plate was subjected to rubbering treatment, the hydrophilic property of the non-image parts was further improved.

EXAMPLE 8 A printing plate making material was produced by dissolving 0. lg of carbon tetrabromide, 0. lg of difurfurylidene pentaerythritol and 0.1g of 4-ethylresorcinol in 3g of a 5% tetrahydrofuran solution of polymethyl methacrylate, and applying the resulting solution to the same support and in the same manner as in Example 6. The thickness of the photosensitive layer was in the range l4 p A printing plate for positive working was produced by exposure to light in the same manner as in Example 7, carrying out heat treatment l 10C) for 30 seconds, and treating thereafter in the same manner as in Example 7.

EXAMPLE 9 Printing plate making materials were produced by dissolving 0.1g of carbon tetrabromide, 0. lg of one of the following furfurylidene acetal compounds and 0. lg of one of the following phenolic compounds in a 5% tetrahydrofuran solution of polyvinyl alcohol (Sebian A-235, Daisel Co., Ltd) and applying the resulting solutions to the same support and in the same manner as in Example 1. The thickness of the photosensitive layer was in the range l4 ,u..

Positive printing plates for positive working were produced by exposing to light in the same manner as in Example 7, carrying out heat treatment at l 10C for a period as described in the following table, and then unexposed areas removed with solvent (plate making treatment).

Phenolic compound Furfurylidcnc acctal Heating compound time (seconds) Catechol Difurfurylidene pentacryth- 120 ritol Catechol Furfurylidcne 2-methyl 2- I furfurylideneiminol ,3- propylene ether Pyrogallol Difurfurylidene pentaeryth- 6O ritol Hydroquinone Difurfurylidene pentacryth I20 ritol 4-Brornorc- Difurfurylidcne pcntacryth 3O sorcinol ritol 4-6-Dichloro re Difurfurylidcnc 60 soreinol pentaerythritol S-Mcthyl Difurfurylidene pcntaeryth- 9O resorcinol ritol 5 Methyl Furfurylidene 2-ethyl-2,- 60 resorcinol hydroxymthyl-l ,3-

propylene ether Z-Methylresor- Difurfurylidene pentacryth- 40 cinol ritol Rcsorcinol Difurfurylidcne pentaeryth 31) ritol Resorcinol Furfurylidcnc bis( p-chloro- 6O henzyl ether) 2-Aminophenol Difurfurylidene pentaerythritol 180 1,-3-Dihydroxy- Difurfurylidene pentaeryth- 30 naphthalene ritol 4-Mcthoxy-az Difurfurylidcnc pcntaeryth- 60 naphthol v ritol 2,4,6-Trihy- Difurfurylidcnc pcntaeryth- 60 droxytolucnc ritol 2,4,6-Trihy- Furfurylidcnc dianisyl ether 60 droxyacetophenonc EXAMPLE 10 A printing plate making material was produced by dissolving 0.1g of carbon tetrabromide, O. 1 g of difurfurylidene pentaerythritol and 0.3g of phloroglueinol in 4g of a 5% ethyl acetate solution of cellulose acetate butyrate and applying the resulting solution to an anodized aluminum plate in the same manner as in Example 6. The thickness of the photosensitive layer wa sin the range 14 a. v i

The printing plate making material was 'exposed to light in .the same manner as in Example 7, heated at 110C and washed with a solution of ethyl alcoholacetone (2:1 by volume) at C for 3 minutes and then with water at 25C for minutes, The plate was then treated in the same plate making treatment as in Example 6, by which a printing plate for positive work-' ing was produced,

EXAMPLE 1 1 A printing plate making material was produced by dissolving O. l of carbon tetrabromide, 0. lg of difurfurylidene pentaerythritol and 0.1g of phloroglueinol in a 5% tetrahydrofuran solution of polyvinyl formal (Denka Formal 3000, Denki Kagaku Kogyo Co., Ltd.) and applying the resulting solution to an anodized aluminum plate in the same manner as in Example 6 This printing plate making material 'was exposed to li'ghtin the same manner as in Example 7', heated at 60C 'for 5 minutes, washed once with ethyl alcohol at 40C for minute, whereupon a printing plate for positive working was produced. The thickness of thephoto sensitive 2 minutes, and then washed with water at for l EXAMPLE 1 2 A printing plate making material was produced by dissolving 0.1g of iodoform, 0.1g of difurfurylidene pentaerythritol and 0.3g of phloroglueinol in a 5% tetrahydrofuran solution of polyvinyl acetate and applying the resulting solution to an anodized aluminum plate in the same manner as in Example 6. The thickness of the photosensitive layer was in the range 14 [L.

A printing plate for positive working was produced by exposing to light, heating and washing in the same manner as in Example 7.

EXAMPLE 13 A printingplate making material was produced by dissolving 0.1g of carbon tetrabromide, 0. lg of 2,5- dihydroxy-benzoic acid and 0. lg of difurfurylidene pentaerythritol in a 5% tetrahydrofuran solution of polyvinyl butyral (same as in Example 6) and applying the resulting solution to an anodized aluminum plate in the same manner as in Example 6. A printing plate for negative working was produced by exposing to light in the same manner as described in Example 6, applying heat by means of a 500 watt infrared ray lamp at 15 em distance for 4 minutes, and then carrying out the plate making treatment in the same manner as in Example 6. The thickness of the photosensitive layer was in the range l4 ,u.

EXAMPLE 1 4 A printing plate making material was produced using 0.1g of a,a,a-p-tetrabromoacetophenone, 0.1g of difurfiirylidene pentaerythritol and 0.1g of phloroglueinol in the same manner as in Example 6. This printing plate making material was exposed to light, heated and treated with solvent in the same manner as in Example 6 to produce a printing plate for positive working. The thickness of the photosensitive layer was in the range 5 EXAMPLE 15 EXAMPLE 1 A printing platc makin'g material was produced by dissolving 0. lg ofa,a,a-tribromomethylphenylsulfone, 0.1g of furfurylidene 2-ethyl-2-hydroxymethyl-1,3- propylcne ether and 0. lg of phloroglueinol in a 5% tetrahydrofuransolution of polyvinyl butyral, and then treating in the same manner as in Example 6. The thickness of the photosensitive layer was in the range I 14 a. The printing plate making material was then exposed tolight, heated and'treated with solvent in order to produce a printing plate for positive working.

Thus, from the above it is seen that thehaloalkane.

- -carbon'atoms, an alkoxy group of 14 carbon atoms, a

and phenol compound react together byexposure, and.

a great amount of halogenic hydrogen formed. The thus formed halogenic hydrogen is used as a catalyst, e.g., ring opening polymerization of the furfurylidene, and acid polycondensation of the phenolic compound and the hydrolysis product of furfurylidene, etc., proceeds. Uniform heating shortens the reaction time of the above.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

What is claimed is:

l. Non-silver salt photo-sensitive materials which consist essentially of a light-sensitive layer containing as image-forming components a high-sensitive haloalkane having a dissociation energy of less than 75 Kcal/mol, a furfurylidene acetal compound of the followiwng formula (Ila) or formula (Ilb):

(Ila) wherein R and R each represents one or two phenyl groups or one or two aralkyl groups, or one or two furfuryl groups;

[I ll CH O wherein R represents an alkylene group having 27 carbon atoms, which can be substituted with a hydroxyalkyl group having l4 carbon atoms or an amino group, or may be dimerized by a spiro carbon, and a phenol compound of formulae (llla) or (Illb) wherein n is an integer of 1-3, and R represents a hydrogen atom, a halogen atom, an alkyl group of l-4 ,carboxyl group, analkoxycarbonyl group of l2 carbon atoms, 'a formyl group, a sulfo group or an acyl group of l4 carbon atoms.

.2. Non-silver salt photo-sensitive material as claimed in claim 1 where the haloalkane is of the formula R--CX wherein X represents a halogen atom (where Xs may differ from each other) or a hydrogen atom (but all Xs cannot be hydrogen atoms), and R represents a hydrogen atom; a halogen atom; an alkyl group having 1-7 carbon atoms; a halogen substituted alkyl group having l-7 carbon atoms; an acyl group; or an acyl group or arysulfonyl group substituted with a halogen atom, a nitro group or an aryl group.

3. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein said haloalkane is carbon tetrabromide, iodoform, carbon tetraiodide, hexachloroethane, hexafluoroethane, 1,2-diiodoethane, bromotriiodomethane or chloro-diiodomethane.

4. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein said furfurylidene acetal is difurfurylidene pentaerythritol, furfurylidene Z-ethyl- 2-hydroxymethyll ,3-propylene-ether, furfurylidene difurfuryl-ether, furfurylidene-2-methyl-2- furfurylideneiminol ,3-propylene-ether, furfurylidenetetramethylethylene-ether, furfurylidene-diphenethylether, furfurylidene-dibenzyl-ether, furfurylidenedianisyl-ether, furfurylidene-dibenzohydrylether or furfurylidene-bis-(p-chlorobenzylether).

5. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein said phenol compound is pyrogallol, methyl gallate, ethyl gallate, n-propyl gallate, isoamyl gallate, lauryl gallate, stearyl gallate, gallic acid, phloroglucinol, 2,4,6-trihydroxy-toluene, 2,4,6- trihydroxy-acetophenone, 3-methoxy-catechol, 2,3,4- dihydroxy-benzoic acid, 2,5-dihydroxy-benzoic acid, 2,6-dihydroxy-3,5di-tert.butyl-benzoic acid, 2,6-dihydroxy-benzaldehyde, 4,5-dihydroxy-toluene, resorcinol, 4-chloro-resorcinol, 3,5-dihydroxy-toluene, hydroquinone, p-hyclroxybenzene-sulfonic acid, pbromophenol, l,5-dihydroxy-naphthalene, 1,3-dihydroxy-naphthalene or 2,7-dihydroxy-naphthalene-3- sulfonic acid.

6. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein the said light-sensitive layer additionally contains a film forming binder.

7. Non'silver salt photo-sensitive materials as claimed in claim 6 where the binder is nitrocellulose, benzyl cellulose, polycarbonate, polyvinyl acetate, cellulose acetate, cellulose acetate butyrate, cellulose acetate phthalate, polyvinyl chloride, polystyrene, polyester, polymethyl methacrylate, polyvinyl pyrrolidone, polyvinyl butyral or polyphenyleneoxide.

8. Non-silver salt photo-sensitive materials as claimed in claim 1 where the weight ratio of the haloalkane to the furfurylidene acetal is 0. l3.

9. Non-silver salt photo-sensitive materials as claimed in claim 8 where the weight ratio is 0.5-2.

l0. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein the weight ratio of the phenol compound to the furfurylidene acetal is 5 or less.

11. Non-silver salt photo-sensitive materials as claimed in claim 10 where the weight ratio is 0.05-2.

l2. Non-silver salt photo'sensitive materials as claimed in claim 1 wherein said light-sensitive haloalkane has the following formula (I):

wherein each X may be same or different and reprealkyl group having -l-3 carbon atoms. 

1. NON-SILVER SALT PHOTO-SENSITIVE MATERIALS WHICH CONSIST ESSENTIALLY OF A LIGHT-SENSITIVE LAYER CONTAINING AS IMAGE-FORMING COMPONENTS A HIGH-SENSITIVE HALO-ALKANE HAVING A DISSOCIATION ENERGY OF LESS THAN 75 KCAL/MOL, A FURFURYLIDENE ACETAL COMPOUND OF THE FOLLOWING FORMULA (IIA) OR FORMULA (IIB):
 2. Non-silver salt photo-sensitive material as claimed in claim 1 where the haloalkane is of the formula R-CX3 (I) wherein X represents a halogen atom (where X''s may differ from each other) or a hydrogen atom (but all X''s cannot be hydrogen atoms), and R represents a hydrogen atom; a halogen atom; an alkyl group having 1-7 carbon atoms; a halogen substituted alkyl group having 1-7 carbon atoms; an acyl group; or an acyl group or arysulfonyl group substituted with a halogen atom, a nitro group or an aryl group.
 3. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein said haloalkane is carbon tetrabromide, iodoform, carbon tetraiodide, hexachloroethane, hexafluoroethane, 1,2-diiodoethane, bromo-triiodomethane or chloro-diiodomethane.
 4. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein said furfurylidene acetal is difurfurylidene pentaerythritol, furfurylidene 2-ethyl-2-hydroxymethyl-1,3-propylene-ether, furfurylidene difurfuryl-ether, furfurylidene-2-methyl-2-furfurylideneimino-1,3-propylene-ether, furfurylidene-tetramethylethylene-ether, furfurylidene-diphenethyl-ether, furfurylidene-dibenzyl-ether, furfurylidene-dianisyl-ether, furfurylidene-dibenzohydrylether or furfurylidene-bis-(p-chlorobenzylether).
 5. Non-silver salt photo-sensitive materials as claImed in claim 1 wherein said phenol compound is pyrogallol, methyl gallate, ethyl gallate, n-propyl gallate, isoamyl gallate, lauryl gallate, stearyl gallate, gallic acid, phloroglucinol, 2,4,6-trihydroxy-toluene, 2,4,6-trihydroxy-acetophenone, 3-methoxy-catechol, 2,3, 4-dihydroxy-benzoic acid, 2,5-dihydroxy-benzoic acid, 2,6-dihydroxy-3,5-di-tert.butyl-benzoic acid, 2,6-dihydroxy-benzaldehyde, 4,5-dihydroxy-toluene, resorcinol, 4-chloro-resorcinol, 3,5-dihydroxy-toluene, hydroquinone, p-hydroxybenzene-sulfonic acid, p-bromophenol, 1,5-dihydroxy-naphthalene, 1,3-dihydroxy-naphthalene or 2,7-dihydroxy-naphthalene-3-sulfonic acid.
 6. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein the said light-sensitive layer additionally contains a film forming binder.
 7. Non-silver salt photo-sensitive materials as claimed in claim 6 where the binder is nitrocellulose, benzyl cellulose, polycarbonate, polyvinyl acetate, cellulose acetate, cellulose acetate butyrate, cellulose acetate phthalate, polyvinyl chloride, polystyrene, polyester, polymethyl methacrylate, polyvinyl pyrrolidone, polyvinyl butyral or polyphenyleneoxide.
 8. Non-silver salt photo-sensitive materials as claimed in claim 1 where the weight ratio of the haloalkane to the furfurylidene acetal is 0.1-3.
 9. Non-silver salt photo-sensitive materials as claimed in claim 8 where the weight ratio is 0.5-2.
 10. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein the weight ratio of the phenol compound to the furfurylidene acetal is 5 or less.
 11. Non-silver salt photo-sensitive materials as claimed in claim 10 where the weight ratio is 0.05-2.
 12. Non-silver salt photo-sensitive materials as claimed in claim 1 wherein said light-sensitive halo-alkane has the following formula (I): R-CX3 (I) wherein each X may be same or different and represents a halogen atom or hydrogen atom, but every X cannot be a hydrogen atom, and R represents a hydrogen atom, a halogen atom or a halogen-substituted alkyl group having 1-3 carbon atoms. 